Azo dyes containing thienothiophene radicals as radicals of the diazo component

ABSTRACT

Thienothiophene dyes of the formula ##STR1## wherein Z is carboxylate, acyl, carboxyl, substituted or unsubstituted carbamoyl, cyano or nitro, X is hydrogen, fluorine, chlorine, bromine, Z or a group of the formula ##STR2## T 1  and T 2  are identical or different and each is independently of the other cyano, substituted or unsubstituted alkoxycarbonyl, alkenyloxycarbonyl, carbamoyl or alkylcarbamoyl and W is hydrogen, methyl or ethyl, Y is hydrogen, chlorine or bromine and K is the radical of a coupling component, are highly suitable for dyeing synthetic fibers, in particular polyesters wherein the dyeing obtained have good fastness properties.

The present invention relates to a thienothiophene dye of the formula I ##STR3## where Z is C₁ -C₈ -alkoxycarbonyl whose alkyl chain may be interrupted by one or more oxygen atoms, or is substituted or unsubstituted phenoxycarbonyl, carbamoyl, C₁ -C₈ -mono-alkylcarbamoyl or -dialkylcarbamoyl, pyrrolidinocarbonyl, piperidinocarbonyl, morpholinocarbonyl, piperazinocarbonyl, (N-C₁ -C₄ -alkyl)piperazinocarbonyl, carboxyl, cyano, C₁ -C₁₀ -alkanoyl, substituted or unsubstituted phenylcarbonyl, C₁ -C₄ -alkylsulfonyl, substituted or unsubstituted phenylsulfonyl or nitro, X is hydrogen, fluorine, chlorine, bromine, Z or a group of the formula --CH═CT¹ T², --CH═N--OH, --CH═N--NH--C₆ H₅ or ##STR4## where T¹ and T² are identical or different and each is, independently of the other, cyano, C₁ -C₈ -alkoxy carbonyl whose alkyl chain may be interrupted by one or more oxygen atoms, or is C₃ -C₆ -alkenyloxycarbonyl, carbamoyl or C₁ -C₄ -mono-alkylaminocarbonyl or -dialkylaminocarbonyl and W is hydrogen, methyl or ethyl, Y is hydrogen, chlorine or bromine and K is the radical of a coupling component.

Any alkyl in the formula of the thienothiophene dye according to the invention may be straight-chain or branched. Where substituted phenyl occurs in the formula of the thienothiophene dye according to the invention, the substituents may be C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halogen, in particular fluorine, chlorine or bromine.

Z and X in the formula I are for example: CHO, CH₃ CO, C₂ H₅ CO, C₃ H₇ CO, C₄ H₉ CO, C₅ H₁₁ CO, C₇ H₁₅ CO, ##STR5## C₆ H₅ CO, CH₃ C₆ H₄ CO, ClC₆ H₄ CO, (CH₃)₂ C₆ H₃ CO, H₃ COC₆ H₄ CO, Cl₂ C₆ H₃ CO, CH₃ SO₂, C₂ H₅ SO₂, C₄ H₉ SO₂, C₆ H₅ SO₂, CH₃ C₆ H₄ SO₂, ClC₆ H₄ SO₂, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₆ H₁₃, COOC₈ H₁₇, ##STR6## COOC₂ H₄ OCH₃, COOC₂ H₄ OC₂ H₅, COOC₂ H₄ OC₄ H₉, COOC₆ H₅, COOC₆ H₄ CH₃, CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₄ H₉, CONHC₆ H₁₃, CONHC₈ H₁₇, CON(CH₃)₂, CON(C₂ H₅)₂, CON(C₄ H₉)₂ or ##STR7##

T¹ and T² in the formula I are for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, secbutoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, sec-pentyloxycarbonyl, tert-pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, 2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 2-butoxyethoxycarbonyl, 3-methoxypropoxycarbonyl, 3,6-dioxaheptyloxycarbonyl, allyloxycarbonyl, 2-methylallyloxycarbonyl, 2-ethylallyloxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl or methyl-ethylaminocarbonyl.

K is derived from a coupling component of the formula HK. This type preferably comes from the aniline, α-naphthylamine, pyrazole, aminopyrazole, indole, thiazole, thiophene, phenol, naphthol, tetrahydroquinoline, pyridone or pyridine series, preference being given to coupling components from the aniline, pyrazole, pyridine, thiophene or thiazole series.

This coupling component HK has the formula ##STR8## where R¹ is hydrogen, C₁ -C₄ -alkyl which may be substituted by phenyl, or substituted or unsubstituted phenyl, R² is hydrogen or R³, R³ is substituted or unsubstituted C₁ -C₆ -alkyl, C₅ -C₇ -cycloalkyl, C₃ -C₄ -alkenyl or substituted or unsubstituted phenyl, R⁴ and R⁵ are each independently of the other hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenoxy, benzyloxy, halogen, C₁ -C₄ -alkylsulfonylamino, C₁ -C₄ -dialkylaminosulfonylamino, substituted or unsubstituted C₁ -C₆ -alkanoylamino, benzoylamino or C₁ -C₄ -alkoxycarbonylamino, R⁶ is cyano, carbamoyl, C₁ -C₄ -monoalkylcarbamoyl or -dialkylcarbamoyl, nitro or C₁ -C₈ -alkoxycarbonyl whose alkyl chain may be interrupted by one or more oxygen atoms, and R⁷ is halogen, nitro, substituted or unsubstituted phenyl, C₁ -C₁₀ -alkyl or C₁ -C₁₀ -alkoxy, where in either case the alkyl chain may be interrupted by one or more oxygen atoms and/or substituted by phenyl, or is phenoxy, C₁ -C₄ -monoalkylamino or -dialkylamino, C₁ -C₄ -alkylthio, phenylthio, C₁ -C₄ -alkoxycarbonyl, C₁ -C₅ -alkanoylamino, C₁ -C₄ -alkoxycarbonylmethyl or cyanomethyl.

Specific examples of R¹, in addition to those already mentioned, are methyl, ethyl, propyl, butyl, benzyl, 2-phenylethyl, phenyl, o-, m- or p-tolyl and o-, m- or p-chlorophenyl.

Examples of R³, in addition to those already mentioned, are C₁ -C₆ -alkyl, which may be monosubstituted or polysubstituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, propargyloxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl.

Specific examples of R³ are methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, 2-phenylethyl, allyl, methallyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-phenyl-2-hydroxyethyl, 2,3-dihydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxy-3-phenoxypropyl, 2-hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, 2-phenoxypropyl, 2-acetoxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 2-isobutyryloxyethyl, 2-methoxymethylcarbonyloxyethyl, 2-ethoxymethylcarbonyloxyethyl, 2-phenoxymethylcarbonyloxyethyl, 2-methoxycarbonyloxyethyl, 2-ethoxycarbonyloxyethyl, 2-propoxycarbonyloxyethyl, 2-butoxycarbonyloxyethyl, 2-phenyloxycarbonyloxyethyl, 2-benzyloxycarbonyloxyethyl, 2-methoxyethoxycarbonyloxyethyl, 2-ethoxyethoxycarbonyloxyethyl, 2-propoxyethoxycarbonyloxyethyl, 2-butoxyethoxycarbonyloxyethyl, 2-methylaminocarbonyloxyethyl, 2-ethylaminocarbonyloxyethyl, 2-propylaminocarbonyloxyethyl, 2-butylaminocarbonyloxyethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 2-propoxycarbonylethyl, 2-butoxycarbonylethyl, 2-phenoxycarbonylethyl, 2-benzyloxycarbonylethyl, 2-β-phenylethoxycarbonylethyl, 2-methoxyethoxycarbonylethyl, 2-ethoxyethoxycarbonylethyl, 2-propoxyethoxycarbonylethyl, 2-butoxyethoxycarbonylethyl, 2-phenoxyethoxycarbonylethyl, 2-benzoylethyl, cyclopentyl, cyclohexyl, cycloheptyl, allyl, methallyl, phenyl, 2-methylphenyl and 4-chlorophenyl.

Where R⁴ and R⁵ are each substituted C₁ -C₆ -alkanoyl amino, suitable substituents are for example, chlorine, bromine, cyano, methoxy, ethoxy or phenoxy. Suitable R⁴ and R⁵, in addition to those already mentioned, are for example hydrogen, methyl, ethyl, propoyl, bromine, chlorine, methoxy, ethoxy, methylsulfonylamino, dimethylaminosulfonylamino, methoxycarbonylamino or ethoxycarbonylamino.

Examples R⁶, in addition to those already mentioned, are methylaminocarbonyl, dimethylaminocarbonyl, ethylaminocarbonyl, diethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, n-, i- or sec-butoxycarbonyl, methoxyethoxycarbonyl, ethoxyethoxycarbonyl, n- or i-propoxyethoxycarbonyl and n-, i- or sec-butoxyethoxycarbonyl.

Examples of R⁷, in addition to those already mentioned, are benzyl, benzyloxy, chlorine, bromine, C₁ -C₄ -alkoxyethoxy, acetylamino, propionylamino, butyrylamino and valerylamino.

Particular importance is given to thienothiophene dyes of the formula I containing coupling components from the aniline, α-naphthylamino, thiazole, thiophene or pyridine series.

Particular preference is given to those thienothiophene dyes of the formula I where X is formyl, acetyl, C₁ -C₄ -alkoxycarbonyl, nitro or cyano, Y is hydrogen, Z is cyano, C₁ -C₂ -alkoxycarbonyl, C₁ -C₂ -monoalkylcarbamoyl, C₁ -C₂ -alkylsulfonyl or phenylsulfonyl, and K is the radical of a coupling component of the aniline, thiazole or pyridine series.

A mention has to be given in particular to those thienothiophene dyes of the formula I where Z is cyano, methoxycarbonyl or ethoxycarbonyl.

To prepare the thienothiophene dye of the formula I, a thienothiophene of the formula II ##STR9## where X, Y and Z each have the abovementioned meanings, can be diazotized and reacted with a coupling component of the formula III

    HK                                                         (III)

where K has the abovementioned meanings, in a conventional manner. Details of the preparation are revealed in the Examples.

The thienothiophene of the formula II can be obtained for example by reacting a thiophene of the formula IV ##STR10## where Z has the abovementioned meanings, with a mercaptan of the formula V

    A--CH.sub.2 --SH                                           (V)

where A is an electron-attracting radical.

The thienothiophene of the formula II were X is hydrogen, fluorine, chlorine or bromine can be obtained by further reaction from the compound of the formula VI ##STR11## where A and Z each have the abovementioned meanings. In the same way, the thienothiophene of the formula II where Y is not hydrogen can be prepared by introducing chlorine or bromine into a compound of the formula VI.

Furthermore, to prepare the thienothiophene dye of the formula I it is also possible to react a thiophene dye of the formula VII ##STR12## where K and Z each have the abovementioned meaning and Hal is halogen with a mercaptan (V). Details can again be found in the Examples.

In those compounds of the formulae I and II where X is formyl, this formyl group can be further reacted in a conventional manner. Possibilities are for example the condensation with hydroxylamine and, if desired, an acylation on the oxygen to form a nitrile or the reaction with phenylhydrazine or with an active methyl compound by Knoevenagel or Perkin.

The thienothiophene dye according to the invention is highly suitable for dyeing synthetic fibers, preferably polyesters and nylons, and blend fabrics of polyesters and cellulose fibers or cellulose esters. The dyeings obtained have good fastness properties, in particular on polyester.

Given a suitable structure, the dye may also be dischargeable under alkaline and/or reducing conditions in a conventional manner.

The Examples which follow illustrate the invention in more detail. The parts and percentages are by weight, unless otherwise stated.

EXAMPLE 1 ##STR13##

A mixture of 18.7 parts of 2-amino-4-chloro-3-cyano-5-formylthiophene, 13.8 parts of potassium carbonate and 80 parts of N,N-dimethylformamide was introduced first, and 9 parts of acetonylmercaptan were then added. After the exothermic reaction had died down, the mixture was heated at 60° C. for 1 hour and then discharged onto water. The precipitate was filtered off with suction, washed with water and dried. This gave 17.9 parts (81% of theory) of 5-acetyl-2-amino-3-cyanothieno[3,2-b]thiophene.

Melting point: 285° C. (decomposition, from methylglycol).

IR (KBr): 3,419, 3,326 (NH₂), 2,205 (CN), 1,654, 1,629 cm⁻¹ C₉ H₆ N₂ OS₂ (222).

Calculated: C: 48.6, H: 2.7, N: 12.6, S: 28.9. Found: C: 48.2, H: 2.8, N: 12.4, S: 28.6.

EXAMPLE 2 ##STR14##

120 parts of ethyl thioglycolate were added to a mixture of 241.5 parts of N,N-dimethyl-N'-(4-chloro-3-cyano-5-formylthien-2-yl)formamidine, 138 parts of potassium carbonate and 1,400 parts of N,N-dimethylformamide. After the slightly exothermic reaction had died down, the reaction mixture was stirred at 50° C. for 2 hours. 1,000 parts of ice, 1,000 parts of water and 150 parts of concentrated hydrochloric acid were then added. The precipitate was filtered off with suction, washed with water and dried. This gave 284 parts (93% of theory) of N,N-dimethyl-N'-(3-cyano-5-ethoxycarbonylthieno[3,2-b]thien-2-yl)formamidine.

Melting point: 168° C. (from glacial acetic acid).

IR (KBr): 2,206 (CN), 1,701, 1,689 (C═O) 1,634, 1,623 cm⁻¹. C₁₃ H₁₃ N₃ O₂ S₂ (307).

Calculated: C: 50.8, H: 4.3, N: 13.7, O: 10.4, S: 20.9. Found: C: 50.9, H: 4.2, N: 13.7, O: 10.4, S: 20.3.

EXAMPLE 3 ##STR15##

A mixture of 319 parts of N,N-dimethyl-N'-(3-cyano-5-ethoxycarbonylthieno[3,2-b]thien-2-yl)formamidine, 2,000 parts of ethanol and 210 parts of concentrated hydrochloric acid was heated at the boil for 1 hour. After cooling down, the precipitate was filtered off with suction, washed with methanol and then with water and dried. This gave 210 parts (80% of theory) of ethyl 2-amino-3-cyanothieno[3,2-b]thiophene-5-carboxylate.

Melting point: 250° C. (from glacial acetic acid).

IR (KBr): 3,418, 3,322 (NH₂), 2,205 (CN), 1,712, 1,694 cm⁻¹. C₁₀ H₈ N₂ O₂ S₂ (252).

Calculated: C: 47.6, H: 3.2, N: 11.1, O: 12.7, S: 25.4. Found: C: 47.6, H: 3.3, N: 11.0, O: 13.1, S: 25.2.

EXAMPLE 4 ##STR16##

25.2 parts of 2-amino-3-cyanothieno[3,2-b]thiophene-5-carboxylate were added to a solution of 11.2 parts of potassium hydroxide, 10 parts of water and 150 parts of ethanol. The mixture was heated at the boil for 2 hours. The precipitate was then filtered off with suction, washed with ethanol and added to dilute hydrochloric acid. The hydrochloric acid suspension was stirred at room temperature for 3 hours. The product was then filtered off with suction and washed with water. Drying left 15 parts (67% of theory) of 2-amino-3-cyanothieno[3,2-b]thiophene-5-carboxylic acid.

Melting point: 280° C. (decomposition).

IR (KBr): 3,421, 3,329 (NH₂), 3,200-2,350 (OH), 2,206 (CN), 1,661, 1,627 cm⁻¹.

C₈ H₄ N₂ O₂ S₂ (224).

Calculated: C: 42.9, H: 1.8, N: 12.5, O: 14.3, S: 28.6. Found: C: 42.5, H: 1.9, N: 12.2, O: 15.3, S: 27.9.

Table 1 below gives 2-aminothieno[3,2-b]thiophenes of the formula ##STR17## which can be obtained in a similar manner.

                  TABLE 1                                                          ______________________________________                                         Example   X             Y     Z                                                ______________________________________                                          5        CN            H     CN                                                6        NO.sub.2      H     CN                                                7        CO.sub.2 CH.sub.3                                                                            H     CN                                                8        CHO           H     CN                                                9        Cl            H     CN                                               10        Br            H     CN                                               11        H             H     CN                                               12        CN            Cl    CN                                               13        COCH.sub.3    H     CO.sub.2 C.sub.2 H.sub.5                         14        CO.sub.2 C.sub.2 H.sub.5                                                                     H     CO.sub.2 C.sub.2 H.sub.5                         15        CN            H     CO.sub.2 C.sub.2 H.sub.5                         16        NO.sub.2      H     CO.sub.2 C.sub.2 H.sub.5                         17        COCH.sub.3    H     CO.sub.2 CH.sub.3                                18        CO.sub.2 CH.sub.3                                                                            H     CO.sub.2 CH.sub.3                                19        CN            H     CO.sub.2 CH.sub.3                                20        C.sub.6 H.sub.5 CO                                                                           H     CN                                               ______________________________________                                    

EXAMPLE 21

5.55 parts of 5-acetyl-2-amino-3-cyanothieno[3,2-b]thiophene were suspended at 0°-5° C. in 75 parts by volume of 3:1 glacial acetic acid/propionic acid and 50 parts by volume of 85% strength sulfuric acid. 8.25 parts of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise with stirring. The mixture was then stirred at 0°-5° C. for 3 hours.

This diazonium salt solution was added at about 0° C. with stirring to a mixture of 5.65 parts of 3-(N,N-diethylamino)-1-acetanilide and 0.5 part of sulfamic acid in 100 parts by volume of N,N-dimethylformamide. The temperature was maintained by external cooling and sprinkling in about 400 parts of ice. The resulting dye suspension was then stirred for 3-4 hours. The dye of the formula ##STR18## was filtered off with suction, washed with water until neutral and dried (9.1 parts). It dyes polyester fiber material in blue shades having very good fastness properties.

The dyes listed in Tables 2 and 3 below can be prepared in a similar manner.

The dyes of Table 2 conform to the formula

                                      TABLE 2                                      __________________________________________________________________________      ##STR19##                                                                                                                       Hue                          Exp.                                                                              X    Y  Z    R.sup.5    R.sup.4                                                                             R.sup.3  R.sup.2  on PES                       __________________________________________________________________________     22 COCH.sub.3                                                                          H  CN   CH.sub.3   H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         reddish                                                                        blue                         23 COCH.sub.3                                                                          H  CN   CH.sub.3   H    C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                         reddish                                                                        blue                         24 COCH.sub.3                                                                          H  CN   NHCOCH.sub.2 Cl                                                                           H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         25 COCH.sub.3                                                                          H  CN   NHCOCH.sub.2 OCH.sub.3                                                                    H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         26 COCH.sub.3                                                                          H  CN   NHCOC.sub.2 H.sub. 5                                                                      H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         27 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              H    C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                         blue                         28 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              OCH.sub.3                                                                           C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         greenish                                                                       blue                         29 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              OC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         greenish                                                                       blue                         30 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              OCH.sub.3                                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             greenish                                                                       blue                         31 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              OCH.sub.3                                                                           C.sub.2 H.sub.4 CN                                                                      CH.sub.2 CHCH.sub.2                                                                     greenish                                                                       blue                         32 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.4 OCH.sub.3                                                               C.sub.2 H.sub.5                                                                         blue                         33 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.4 OCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                               blue                         34 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              H    C.sub.4 H.sub.8 OCOCH.sub.3                                                             C.sub.4 H.sub.8 OCOCH.sub.3                                                             blue                         35 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              H    CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CHCH.sub.2                                                                     blue                         36 COCH.sub.3                                                                          H  CN   NHCOCH.sub.2 CN                                                                           H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         37 COCH.sub.3                                                                          H  CN   NHCOCH.sub.2 C.sub.6 H.sub.5                                                              H    n-C.sub.3 H.sub.7                                                                       n-C.sub.3 H.sub.7                                                                       blue                         38 COCH.sub.3                                                                          H  CN   CH.sub.3   H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 OH                                                                      reddish                                                                        blue                         39 COCH.sub.3                                                                          H  CN   CH.sub.3   H    C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                      reddish                                                                        blue                         40 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             navy                         41 COCH.sub.3                                                                          H  CN   CH.sub.3   OCH.sub.3                                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             blue                         42 COCH.sub.3                                                                          H  CN   H          H    C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.5                                                                         bluish                                                                         violet                       43 COCH.sub.3                                                                          H  CN   NHSO.sub.2 CH.sub.3                                                                       H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         44 COCH.sub.3                                                                          H  CN   NHCOC.sub.2 H.sub.5                                                                       H    C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                      blue                         45 COCH.sub.3                                                                          H  CN   H          OCH.sub.3                                                                           C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         46 COCH.sub.3                                                                          H  CN   CH.sub.3   H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 CN                                                                      bluish                                                                         violet                       47 COCH.sub.3                                                                          H  CN   NHCOOC.sub.2 H.sub.5                                                                      H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 OH                                                                      reddish                                                                        red                          48 COCH.sub.3                                                                          H  CN   H          OCH.sub.3                                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             blue                         49 COCH.sub.3                                                                          H  CN   NHCOCH(CH.sub.3).sub.2                                                                    H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         50 COCH.sub.3                                                                          H  CN   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.5                                                                         reddish                                                                        blue                         51 COCH.sub.3                                                                          H  CO.sub.2 C.sub.2 H.sub.5                                                            NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         52 COCH.sub.3                                                                          H  CO.sub.2 C.sub.2 H.sub.5                                                            NHCOC.sub.2 H.sub.5                                                                       CH.sub.3                                                                            n-C.sub.3 H.sub.7                                                                       n-C.sub.3 H.sub.7                                                                       blue                         53 COCH.sub.3                                                                          H  CO.sub.2 C.sub.2 H.sub.5                                                            NHCOCH.sub.2 OCH.sub.3                                                                    H    C.sub.2 H.sub.4 OCH.sub.3                                                               C.sub.2 H.sub.4 OCH.sub.3                                                               blue                         54 COCH.sub.3                                                                          H  CO.sub.2 C.sub.2 H.sub.5                                                            NHCOCH.sub.3                                                                              OCH.sub.3                                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             greenish                                                                       blue                         55 COCH.sub.3                                                                          H  CO.sub.2 C.sub.2 H.sub.5                                                            CH.sub.3   H    C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.5                                                                         bluish                                                                         violet                       56 COCH.sub.3                                                                          H  CO.sub.2 C.sub.2 H.sub.5                                                            H          H    C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.4 OCOCH.sub.3                                                             violet                       57 COCH.sub.3                                                                          H  CO.sub.2 CH.sub.3                                                                   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         58 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.3                                                                              H    n-C.sub.4 H.sub.9                                                                       n-C.sub.4 H.sub.9                                                                       reddish                                                                        blue                         59 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                      reddish                                                                        blue                         60 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.2 OC.sub.6 H.sub.5                                                             H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         reddish                                                                        blue                         61 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   CH.sub.3   H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         voilet                       62 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   H          H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         voilet                       63 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                         reddish                                                                                 blue                         64 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.3                                                                              OCH.sub.3                                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             blue                         65 CO.sub.2 CH.sub.3                                                                   H  CN   NHCOCH.sub.3                                                                              H    n-C.sub.3 H.sub.7                                                                       n-C.sub.3 H.sub.7                                                                       reddish                                                                        blue                         66 CO.sub.2 CH.sub.3                                                                   H  CN   CH.sub.3   H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 CN                                                                      violet                       67 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   CH.sub.3   OCH.sub.3                                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             blue                         68 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   CH.sub.3   H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 OH                                                                      reddish                                                                        blue                         69 CO.sub.2 C.sub.2 H.sub.5                                                            H  CO.sub.2 C.sub.2 H.sub.5                                                            NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         reddish                                                                        blue                         70 CO.sub.2 C.sub.2 H.sub.5                                                            H  CO.sub.2 C.sub.2 H.sub.5                                                            CH.sub.3   H    C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                      reddish                                                                        blue                         71 CO.sub.2 C.sub.2 H.sub.5                                                            H  CO.sub.2 C.sub.2 H.sub.5                                                            CH.sub.3   H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.4 CN                                                                      violet                       72 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.3                                                                              H    C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                         reddish                                                                        blue                         73 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOC.sub.2 H.sub.5                                                                       H    C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4                                                                         bluishsub.3                                                                    violet                       74 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.2 OCH.sub.3                                                                    H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         75 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   H          H    C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.5                                                                         violet                       76 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   CH.sub.3   H    C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.5                                                                         violet                       77 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.3                                                                              OCH.sub.3                                                                           C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         greenish                                                                       blue                         78 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         79 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.4 OH                                                                      blue                         80 CO.sub.2 C.sub.2 H.sub.5                                                            H  CN   NHCOCH.sub.3                                                                              H    C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.5                                                                         reddish                                                                        blue                         81 NO.sub.2                                                                            H  CN   NHCOCH.sub.3                                                                              H    C.sub.3 H.sub.7                                                                         C.sub.3 H.sub.7                                                                         blue                         82 NO.sub.2                                                                            H  CN   NHCOCH.sub.3                                                                              OCH.sub.2 H.sub.5                                                                   C.sub.2 H.sub.4 CN                                                                      CH.sub.2 CHCH.sub.2                                                                     greenish                                                                       blue                         83 NO.sub.2                                                                            H  CN   NHCOCH.sub.3                                                                              H    CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CHCH.sub.2                                                                     blue                         84 NO.sub.2                                                                            H  CN   NHCOCH.sub.2 OCH.sub.3                                                                    H    C.sub.2 H.sub.4 OCOCH.sub.3                                                             C.sub.2 H.sub.4 OCOCH.sub.3                                                             blue                         85 NO.sub.2                                                                            H  CN   NHCOCH.sub.2 Cl                                                                           H    C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                         blue                         86 NO.sub.2                                                                            H  CN   CH.sub.3   H    C.sub.2 H.sub.4 OH                                                                      C.sub.2 H.sub.5                                                                         reddish                                                                        blue                         87 H    H  CN   NHCOCH.sub.3                                                                              H    C.sub.4 H.sub.9                                                                         C.sub.4 H.sub.9                                                                         violet                       88 Cl   H  CN   H          C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         voilet                                89 CN   Cl CN   CH.sub.3   H    C.sub.2 H.sub.4 CN                                                                      C.sub.2 H.sub.5                                                                         voilet                       90 COCH.sub.3                                                                          H  CO.sub.2 C.sub.2 H.sub.5                                                            NHCOCH.sub.2 Cl                                                                           H    C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         blue                         __________________________________________________________________________

The dyes of Table 3 conform to the formula

                  TABLE 3                                                          ______________________________________                                          ##STR20##                                                                                                       Hue                                          Exp.                              on                                           No.  K                            PES                                          ______________________________________                                         91                                                                                   ##STR21##                   blue                                         92                                                                                   ##STR22##                   blue                                         93                                                                                   ##STR23##                   blue                                         94                                                                                   ##STR24##                   blue                                         95                                                                                   ##STR25##                   blue                                         96                                                                                   ##STR26##                   blue                                         97                                                                                   ##STR27##                   blue                                         98                                                                                   ##STR28##                   blue                                         99                                                                                   ##STR29##                   blue                                         100                                                                                  ##STR30##                   blue                                         101                                                                                  ##STR31##                   blue                                         102                                                                                  ##STR32##                   blue                                         103                                                                                  ##STR33##                   vio- let                                     104                                                                                  ##STR34##                   red- dish vio- let                           105                                                                                  ##STR35##                   blu- ish vio- let                            ______________________________________                                    

EXAMPLE 106

0.57 part of p-dithiane-2,5-diol and 0.7 part of potassium carbonate were added to 2.08 parts of 4-chloro-3-cyano-5-formyl-2-(4'-N,N-dibutylamino-2'-methylphenylazo)thiophene in 50 parts by volume of N,N-dimethylformamide. The reaction mixture was stirred at 50° C. under N₂ for 4 hours and then poured onto 500 parts of water. The dye was salted out with NaCl, filtered with suction and washed with water. This gave 1.8 parts of the dye of the formula ##STR36## which dyes polyester fibers in blue, fast shades.

EXAMPLE 107

1.35 parts of 30% strength methanolic sodium methylate solution and 0.9 part of ethyl mercaptoacetate were added to 2.3 parts of 4-chloro-3-cyano-5-formyl-2-(4'-N,N-dibutylamino-2'-acetylaminophenylazo)thiophene in 60 parts by volume of methanol and 50 parts by volume of N,N-dimethylformamide. The mixture was stirred at 25° C. for 10 hours and then at 50° C. for 2 hours and was then discharged onto 500 parts of water. The product was salted out with NaCl, filtered off with suction and washed with water. This gave 2.5 parts of the dye described in Example 58.

EXAMPLE 108

1.75 parts of the dye described in Example 106 were stirred at 25° C. with 0.9 part of ethyl cyanoacetate in 70 parts by volume of dioxane, 0.5 part by volume of glacial acetic acid and 0.5 part by volume of piperidine for 24 hours. 25 parts of water and 25 parts of ice were then added. After 15 minutes of stirring, the product was filtered off with suction and washed until neutral. Drying under reduced pressure at 40° C. left 1.7 parts of the dye of the formula ##STR37## which dyes polyester fibers in greenish blue shades.

Table 4 lists dyes of the formula ##STR38## which can be obtained in a similar manner.

                                      TABLE 4                                      __________________________________________________________________________                                       Hue                                          Exp.                                                                              X   Y Z    R.sup.5                                                                               R.sup.4                                                                            R.sup.3                                                                             R.sup.2                                                                            on PES                                       __________________________________________________________________________     109                                                                               CHO H CN   NHCOCH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    blue                                         110                                                                               CHO H CN   NHCOC.sub.2 H.sub.5                                                                   H   C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    blue                                         111                                                                               CHO H CN   CH.sub.3                                                                              H   C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    reddish                                                                        blue                                         112                                                                               CHO H CO.sub.2 C.sub.2 H.sub.5                                                            NHCOC.sub.2 H.sub.5                                                                   H   n-C.sub.4 H.sub.9                                                                   n-C.sub.4 H.sub.9                                                                  blue                                         113                                                                               CHO H CN   CH.sub.3                                                                              H   C.sub.2 H.sub.4 CN                                                                  C.sub.2 H.sub.5                                                                    blue                                         114                                                                               CHO H CN   NHCOCH.sub.3                                                                          OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    greenish                                                                       blue                                         115                                                                               X*  H CN   CH.sub.3                                                                              H   C.sub.2 H.sub.4 CN                                                                  C.sub.2 H.sub.5                                                                    blue                                         116                                                                               X** H CN   H      H   C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    blue                                         117                                                                               X*  H CN   CH.sub.3                                                                              H   n-C.sub.4 H.sub.9                                                                   n-C.sub.4 H.sub.9                                                                  greenish                                                                       blue                                         __________________________________________________________________________      ##STR39##                                                                      ##STR40##                                                                 

We claim:
 1. A thienothiophene dye of the formula I ##STR41## where Z is C₁ -C₈ -alkoxycarbonyl or C₁ -C₈ alkoxycarbonyl whose alkyl chain is interrupted by one or more oxygen atoms, or is C₁₋₄ alkyl, C₁₋₄ alkoxy or halogen substituted phenoxycarbonyl or unsubstituted phenoxycarbonyl, carbamoyl, C₁ -C₈ -mono-alkylcarbamoyl or -dialkyl-carbamoyl, pyrrolidinocarbonyl, piperidinocarbonyl, morpholinocarbonyl, piperazinocarbonyl, (N-C₁ -C₄ -alkyl)piperazinocarbonyl, carboxyl, cyano, C₁ -C₁₀ -alkanoyl, C₁₋₄ alkyl, C₁₋₄ alkoxy or halogen substituted phenylcarbonyl or unsubstituted phenylcarbonyl, C₁ -C₄ -alkylsulfonyl, C₁₋₄ alkyl, C₁₋₄ alkoxy or halogen substituted phenylsulfonyl or unsubstituted phenylsulfonyl or nitro, X is hydrogen, fluorine, chlorine, bromine, Z or a group of the formula --CH═CT¹ T², --CH═N--OH, --CH═N--NH--C₆ H₅ or ##STR42## where T¹ and T² are identical or different and each is, independently of the other, cyano, C₁ -C₈ -alkoxy carbonyl or C₁ -C₈ -alkoxycarbonyl whose alkyl chain is interrupted by one or more oxygen atoms, or is C₃ -C₆ -alkenyloxycarbonyl, carbamoyl or C₁ -C₄ -monoalkylaminocarbonyl or -dialkylaminocarbonyl and W is hyrogen, methyl or ethyl, Y is hydrogen, chlorine or bromine and K is the radical of a coupling component.
 2. A thienothiophene dye as claimed in claim 1 where K is derived from a coupling component of the formula ##STR43## where R¹ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ alkyl substituted by phenyl, or C₁₋₄ alkyl, C₁₋₄ alkoxy or halogen substituted phenyl or unsubstituted phenyl, R² is hydrogen or R³, R³ is C₁ -C₆ -alkyl, or C₁ -C₆ -alkyl substituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, propargyloxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl; C₅ -C₇ -cycloalkyl, C₃ -C₄ -alkenyl or C₁₋₄ alkyl, C₁₋₄ alkoxy or halogen substituted phenyl or unsubstituted phenyl, R⁴ and R⁵ are each independently of the other hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, phenoxy, benzyloxy, halogen, C₁ -C₄ -alkylsulfonylamino, C₁ -C₄ -dialkylaminosulfonylamino, C₁ -C₆ -alkanoylamino, or C₁ -C₆ -alkanoylamino substituted by chlorine, bromine, cyano, methoxy, ethoxy, phenoxy, hydrogen, methyl, ethyl, propyl, methylsulfonylamino, dimethylaminosulfonylamino, methoxycarbonylamino or ethoxycarbonylamino; benzoylamino or C₁ -C₄ -alkoxycarbonylamino, R⁶ is cyano, carbamoyl, C₁ - C₄ -monoalkylcarbamoyl or -dialkylcarbamoyl, nitro or C₁ -C₈ -alkoxycarbonyl or C₁ -C₈ -alkoxycarbonyl whose alkyl chain is interrupted by one or more oxygen atoms, and R⁷ is halogen, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy, or halogen substituted phenyl or unsubstituted phenyl, C₁ -C₁₀ -alkyl or C₁ -C₁₀ -alkoxy or C₁ -C₁₀ -alkyl or C₁ -C₁₀ -alkoxy wherein the alkyl chain is interrupted by one or more oxygen atoms or substituted by phenyl, or is phenoxy, C₁ -C₄ -monoalkylamino or -dialkylamino, C₁ -C₄ -alkylthio, phenylthio, C₁ -C₄ -alkoxycarbonyl, C₁ -C₅ -alkanoylamino, C₁ -C₄ -alkoxycarbonylmethyl or cyanomethyl.
 3. A thienothiophene dye as claimed in claim 1, wherein X is formyl, acetyl, C₁ -C₄ -alkoxycarbonyl, nitro or cyano, Y is hydrogen, Z is cyano, C₁ -C₂ -alkoxycarbonyl, C₁ -C₂ -monoalkylcarbamoyl, C₁ -C₂ -alkylsulfonyl or phenylsulfonyl, and K is an aniline, thiazole or pyridine radical.
 4. The method of using a compound as claimed in claim 1 for dyeing synthetic fibers.
 5. The thienothiophene dye as claimed in claim 2, wherein R³ is C₁₋₆ alkyl, said C₁₋₆ alkyl being monosubstituted or polysubstituted by chlorine, bromine, hydroxyl, C₁ -C₈ -alkoxy, propargyloxy, phenoxy, phenyl, cyano, carboxyl, C₁ -C₈ -alkanoyloxy, C₁ -C₈ -alkoxy-C₁ -C₄ -alkoxy, benzoyloxy, o-, m- or p-methylbenzoyloxy, o-, m- or p-chlorobenzoyloxy, C₁ -C₈ -alkoxyalkanoyloxy, phenoxyalkanoyloxy, C₁ -C₈ -alkoxycarbonyloxy, C₁ -C₈ -alkoxyalkoxycarbonyloxy, benzyloxycarbonyloxy, phenethyloxycarbonyloxy, phenoxyethoxycarbonyloxy, C₁ -C₈ -alkylaminocarbonyloxy, cyclohexylaminocarbonyloxy, phenylaminocarbonyloxy, C₁ -C₈ -alkoxycarbonyl, C₁ -C₈ -alkoxyalkoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl, phenoxy-C₁ -C₄ -alkoxy or phenethyloxycarbonyl.
 6. The thienothiophene dye as claimed in claim 2, wherein R⁴ and R⁵ are, independently, C₁₋₆ -alkanoylamino, wherein said C₁₋₆ -alkanoylamino is substituted by chlorine, bromine, cyano, methoxy, ethoxy, phenoxy hydrogen, methyl, ethyl, propyl, methylsulfonylamino, dimethylaminosulfonylamino, methoxycarbonylamino or ethoxycarbonylamino. 